DE1669809B2 - USE OF OLIGOMERS AS ADDITIVES TO POLYMERS TO REDUCE ELECTROSTATIC CHARGABILITY - Google Patents

Description

with an average molecular weight of up to 10 ⁴ , where r>

/, m and η are greater than 1,

Y and Z can be the same or different and

Hydrogen, halogen, amino, methoxy,

Nitrile, phenyl, alkyl, alkenyl, thio

ether or alkyl ester groups, R is hydrogen or the methyl group,

X halogen, a phenyl, phenyl sulfone

acid, phenyl sodium sulfonate or

Carboxyl group,
Q and q, which can be the same or different,

Hydrogen, a carboxyl, carbamyl,

Hydroxyl, N-methylolcarbamyl,

Ci- C ₂₀ - alkyl ester,

Hydroxy-Ci-Cralkyl-,

one through the leftovers

-CH ₂ N (CHj) ₃ Cl, -N (C ₂ Hs) ₃ Cl

or by the phosphoric acid, phosphorous acid, phosphonamide, sulfonic acid, Sodium sulfonate, sulfonic acid stannate, sulfonamide, methyl sulfonate residues substituted phenyl group or a quaternary ammonium salt of the pyridine group or the

- COOC ₂ H ₄ - N (CIXC ₂ H ₅ ) 3 group

mean,

or together the cyclic dicarboximide or the cyclic N-methylol dicarboximide group form,

as an additive to be incorporated into compatible polymers to reduce the electrostatic Chargeability.

2. The method according to claim 1, characterized in "> o indicates that the compatible resin is polystyrene, polyvinyl chloride, ABS (acrylonitrile-butadiene-styrene) resin or AS (acrylonitrile styrene) resin is used.

J (I

j

The invention relates to reducing the electrostatic chargeability of polymers by w> incorporation of oligomers with certain polar groups in these polymers.

Usually provide polymers good dielectrics represents nd synthetic resins and Harzpreßlinge and larzfolien tend to even a slight friction or to be charged lektrostatisch with other materials during the lerstellung, storage or use of b ^r> ierührung. This presents numerous difficulties and problems for industrial production and process. However, this disadvantage is one of the properties inherent in polymers and which is inevitable.

Many attempts have already been made to prevent or prevent the electrostatic charging of polymers; however, none of the methods proposed for this purpose has completely eliminated this disadvantage. Since the procedures that have been common in practice up to now can be roughly divided into two groups:

1) Application, adsorption or precipitation of surface-active agents or the like onto the resin surfaces (Fittings or foils).

2) Knead the resins with surfactants or certain other additives.

In principle, these methods should have sufficient surface conductivity for high molecular weight substances can be achieved in order to exclude the formation of static electricity therein.

The desired effect can be expected, for example, from a method according to which a substance with a hydrophilic residue in the molecule mixed with or on a polymeric material as an antistatic agent the surface of which is precipitated.

The methods of group 1) above are mainly used when using very water-soluble surfactants applied. The antistatic effect achieved by this is true noteworthy, but short-lived, as these funds are easily washed off or rubbed off what with is associated with a corresponding reduction in effectiveness. Also, some procedures go for the antistatic treatment often with adverse effects such as increased adhesion and hardening of the treated Surface, hand in hand.

So it is known according to the method of DT-PS 10 47 374, for the antistatic treatment of fibers hydrophobic plastics water-soluble salts of low molecular weight vinyl polymers with a variety of sulfo groups, preferably together with water-soluble fluxes, the higher paraffinic Contains residues to apply to the fiber. The final coating obtained in this way goes on the fibers due to its solubility in water the first time it is washed with water. According to GB-PS 7 86 953 it is already known to improve the processability before artificial staple fibers, the staple fibers with a r Salt of a low molecular weight sulfo group contains the polymer, if appropriate in the presence of an acid to impregnate, whereby the polymer coating formed on the fiber during drying does not start the fiber may stiffen so as not to impair their further processing.

The methods of the group <2) listed above show deficiencies even if the processing time is long since there is a tendency towards phase separation and exudation of the additives over time the surface exists, which sometimes leads to deterioration of properties such as mechanical strength of the product. The proposal to see hygroscopic inorganic salts as antistatic Using active additives for kneading with high molecular weight substances is common practice because of the many difficulties such as chemical Attack effect on the kneading device and contamination of other materials, not in the process feasible.

Other suggestions include increasing the moisture content of the compositions on a physical basis Paths and dissipation of electrostatic charge through irradiation. However, none of them has proven beneficial.

As discussed above, the \ above are Measures are invariable and are not considered ideal because they are either temporary, but non-permanent effects or quite permanent effects are achieved, which then however on There is a cost in the physical or other properties of the resins.

The invention relates to the use of oligomers the general formula:

CH ₂ -CH
X

R.
CH-C

Q q

having an average molecular weight of 10 ² to 10 ⁴ , where

/, m and η are greater than 1,

Y and Z can be identical or different and are hydrogen, halogen, amino, methoxy, Nitrile, phenyl, alkyl, alkenyl, thioether or alkyl ester groups,

R is hydrogen or the methyl group,

X halogen, a phenyl, phenylsulfonic acid,

Phenyl sodium sulfonate or carboxyl group,

Q and q, which can be the same or different, are hydrogen, a carboxyl, carbamyl, hydroxyl, N-methylolcarbamyl,
Ci - C ₂ o-alkyl ester, hydroxy-C, -Cj-alkyl, one through the radicals

-CH ₂ N (CHj) ₃ Cl, -N (C ₂ H ₅ J ₃ Cl

or by the phosphoric acid, phosphorous acid, phosphonamide, sulfonic acid, sodium sulfonate, Substituted sulfonic acid stannate, sulfonamide, methyl sulfonate radicals Phenyl group or a quaternary ammonium salt of the pyridine group or the

-COOC ₂ H ₄ -N (C1XC ₂ H ₅ ) ₃ group

mean,

or together the cyclic dicarboximide or the cyclic N-methylol dicarboximide group form,

as an additive to be incorporated into compatible polymers to reduce the electrostatic Chargeability.

A characteristic of the oligomers used according to the invention as antistatic agents for polymers is that these Oligomers comprise two groups of different functions in one molecule, one of which is group in the chemical structure of the polymer to be treated must be similar and the necessary compatibility to ensure between the polymer and the antistatic additive and the other group of Is a carrier of the antistatic properties.

Are the oligomers used according to the invention in the resins that protect against electrostatic charges should be protected, incorporated, z. B. by tilting, then you get mixtures that are uniform and are resistant in composition and provide safe and permanent protection against electrical ι have chargeability.

In contrast, low molecular weight, antistatic additives only have a short lifespan. They tend to bleed out and then only act as impurities.

in high molecular weight polymers with strongly pronounced On the other hand, antistatic properties or uniformly structured oligomers show a high level of incompatibility with the resin on.

Both disadvantages are avoided with the use of the oligomers according to the invention. If not that Mixing ratios for some special purposes are changed by adding such oligomers only minor changes in mechanical properties, thermal stability, tinting and

2Ii caused transparency of the resin substances contained.

The electrostatic chargeability of these blended resin compositions is determined by a mechanism limited, which reduces their specific surface resistance and surface dissipation of the elektrosta'.ischsn Charging enabled. It is therefore desirable to have a compact in the atmosphere under normal humidity conditions, e.g. B. at a humidity of 50 to 80% a specific

id have surface resistivity of not more than 10 'Ώ should.

Mixing two or more different types of resin compositions with each other is used mechanically with the help of various apparatuses, in

> 5 in many cases by melting the materials together at relatively high temperatures. But you can also use the powdered polymers in mix appropriately, dissolve the obtained mixture homogeneously in an ordinary solvent,

4 (i drip the solution in a nonsolvent to precipitate allow the polymer in a thoroughly mixed state and then separate the precipitate and Refine to the final state of the dry powder.

For mixed resins, an even distribution of the individual components is essential, and so are the problems are usually in the compatibility wedge of the components. Oligomers by nature can make compositions as stated above, in which they are mixed with the resins with which they are mixed should, are very tolerable.

In general, however, the introduction of certain polar groups in such high concentrations that are likely to be sufficient to impart certain additional properties to the oligomers considerable changes, often in that they make the blended resins unacceptable, even if these solvents are very compatible due to the similarity in the basic structure can.

no The oligomers used according to the invention do not become electrostatic when rubbing or - if at all - then only to a negligible extent charged. They can be mixed into resin compositions with which they are compatible in order to achieve the

<, <-, electrostatic charging of the mixtures with success to prevent. Resin compositions here can be of simple composition, such as polystyrenes and resins Polyacrylic ester (e.g. methyl methacrylate) and copo-

polymerized resin materials such as ABS resins.

The proportions in which the oligomers are added depend somewhat on the structure of the resins. It is advisable to optimal proportions (preferably 0.1 to 20 wt .-%) in view of the expected

at

Oligo-styrene-polycarboxylic acid with a polymerization grid of 27.6 and a percentage of 48 carboxyl groups was used in varying amounts of 10 and 5 wt .-% polystyrene added, the components mixed evenly and made into sheets of 1 to 3 mm thick pressed. With a magnetic stick, a predetermined amount of iron dust was drawn out as a grinding

Table 1

Resin properties, molding conditions, application areas and cost.

The method according to the invention will be further described in connection with the examples however, they are used for illustration purposes only and are not intended to infer any restrictions.

play material at its tip and turn it with you κι a predetermined speed on the foils in order to carry out an electrostatic charge of the samples. The charge was determined with a sector field intensity meter (cf. J. Chem. Soc. Japan [Kogyo Kagaku Zasshi] 69 [1966], pages 1351-1355). The results obtained are shown in Table 1.

Sample*) Special surface
resistance (U) ΙΟ ⁶ mm Hg Surface potential (V) air 10 ³ mm Hg in air 3 · 10 '" in up to ± 2 10 to 20 10% additives 4 · 10 ⁹ 8th· ΙΟ ¹⁰ 0 up to ± 2 10 to 20 5% additives 5 · 10 ⁹ 0 5 to 10 After washing with
water 0

*) All samples were washed in water at 40 to 50 C for 5 minutes while rubbing with cheesecloth.

A known method was used for the qualitative determination of the antistatic effect achieved; d. that is, the surface of the sheet-like sample was violently for about 20 seconds with a woolen cloth or fur rubbed and tobacco ash brought to the foil at a distance of 1 to 2 mm to check whether the Sample could attract (+) or not (-) the ashes. In this example, there was no such attraction observed.

Example 2
Oligo-styrene-polymethylol of the general formula:

JO

Cl ₃ C-

- -Ah, -ch \ -4 ch ₂ ch

CH ₂ OH

-NH,

4 ¹ p

Tabel

in which η ss 46 and the ratio of m / l is 13:33, different amounts of 2 and 5 parts to 100 parts of polystyrene were added, both evenly mixed with one another and pressed into sheets. The films obtained in this way were further treated in the same manner as is described in Example 1. The 55 sample results are given in Table 2. The tobacco ash test showed that the samples were not chargeable.

Table 2

(Determination of the values at room temperature)

Example 3

A cooligomer with a methyl methacrylate-acrylic acid ratio of about 60:40 and an average MW of about 9500 (corresponds to sample I of table 3) and another product with an average MW of about 11,000 and an ester-amide ratio of 50:50, which is produced by partial amidation of the ester group of methyl methacrylate in liquid ammonia in The presence of a sodium amide catalyst (corresponds to sample II of Table 3) was used in an amount of 1 part per 100 parts of polymethyl methacrylate was added. All mixtures obtained were thoroughly kneaded and pressed into a film. The samples thus obtained were tested for chargeability examined. The results are shown in Table 3. In the tobacco ash test, they did not attract the ashes nor did they lose the transparency property of the polymethacrylic resin. They also kept the dynamic ones as well as other properties unchanged.

Special surface tobacco surface ash test
surface friction resistance potential

Ui) (V)

sample Special surface Surfaces- W)
(D Additives 5 · 10 " 0 to ± 40 (-) resistance potential (Π) Additives 8th· K) ¹² Obis ± 30 (-) (U) (V) (D 3 times 3 · K) ¹ " 0 to ± 18 (-) 2 parts additives 3 x 10 " 2 to 12 b ^r )
(II) 3m: il ge 5- K) ¹ " 0 to ± 0 (-) 5 parts additives 1 · K) ¹ " 5 to K) to wash Washed 5 times 5 K) ⁹ 0 Poly-MMA 1 · K) ¹ * -380 (+)

Example 4

Of the derivatives of the cooligomer of the structural formula given above, were:
an oligomer (corresponds to sample III of table 4, the other derivatives described below correspond to samples IV to X of the same table), in which

R, Y and Z hydrogen,

X is a phenyl group and

q and Q are carboxyl groups,

an oligomer wherein

q and Q carbamoyl groups
Sample IV),

an oligomer wherein

q and Q are hydroxyl groups or hydroxyl groups with an alkyl group of 1 to 3 carbon atoms are connected, represent (sample V),

an oligomer wherein

q and Q form a cyclic imide (sample VI),

are (corresponds to an oligomer in which

q and Q are imide-methylols (sample VII),

an oligomer wherein either

q or Q is a carboxyl group and the other is an ester group with 1 to 3 carbon atoms represents (sample VIII),

an oligomer wherein either

q or Q is a carboxyl group and the other is a carbamoyl group (Sample IX) as

an oligomer wherein either

q or Q is a carboxyl group and the other is an N-methylolcarbamoyl group (Sample X),

given in different amounts to 100 parts of polystyrene and the resulting mixtures on their Chargeability examined. The results are shown in Table 4.

Table 4

Determination of the values in air at room temperature

sample Part per lOOTeilc resistance Surfaces- Tobacco ash Polystyrene frictional test Cooligomcr- potcntial structure 6th 3 αϊ) (V) III 1 5-10 ¹⁰ 0 to 78 (-) IV 5 3-10 ¹ " 20th (-) V 1 7-10 " 40 to 100 (-) Vl lü 5-10 "' 10 to 100 (-) VII 3 5 x 16 '° 0 to 40 (-) VIII 1 3 · lü " 10 to 40 (-) IV 5 ■ K) ¹ " 0 to ± 50 (-) X 5 · H) " 0 to ± 50 (-)

Example 5

It have differed from the derivatives of cooligomers from maleic anhydride or fumaric anhydride and Vinyl chloride and the oligomer wherein

Y, Z uw'j R hydrogen,

X chlorine and

q and Q are carboxyl groups (corresponds to Sample XI in Table 5, while the others Oligomers are designated with the following numbers in the same table),

an oligomer wherein

Q and q are hydroxyl groups or hydroxyl groups with an alkyl group with 1 to 3 carbon atoms are connected, represent (sample XII) or

an oligomer wherein either

Q or q is a carboxyl group and the other is an ester group formed from an alkyl group with 1 to 2 carbon atoms (sample XlII),

Proven to be very effective antistatic agents for polyvinyl chloride (PVC). In particular the substances, di < have a relatively high concentration of hydrophilic groups and contain ester groups, derei Main chain parts relatively short (up to molecular weights of the order of thousands) and voi of suitable length (e.g. ester groups formed from alkyl radicals of 1 to 20 carbon atoms) have gud Plasticity and remarkable antistatic effects.

Thereafter, the Cooligomerc Xl, XII and XIII i different parts per 100 parts of polyvinyl chloride added. The antistatic effects obtained are shown in Table 5.

709 647 /:

Table 5

sample

Cooligomer structure

Xl

XlI

XIII

Parts per lOOTcile PVC

resistance

(U)

6 · 10 '"5 · K) ¹ " 5-10 "surface

frictional

potential

(V)

-IO to -50
-H) to -60
-30 to -60

Tu bakiiseh litest

Example 6

A derivative of the structure of the general formula ( I) in which X is phenyl and phenylsulphonic acid, ie a derivative of parasulphonic acid of the phenyl group of oligostyrene (XIV), a derivative in which

Y, Z and R hydrogen,

Q is a carboxyl group and

Table 6
sample

Cooligomers

per lüOTeile Sullbnylgruppc

Polystyrene i _n phenyl

added _GRU p _pe amount

(Parts)

q is the butyl carboxylate (prob <

XV),

as well as derivatives of the types in which the acid residues of samples XIV and XV are converted into the sodium salts are (samples XVI and XVII), were in the example I treated way. The results obtained are shown in Table 6.

Ratio of resistance introduction of laziness

Surface

frictional

potential

Tiibakuschetest

XIV

XV

XVI
XVU

2
5

5
5

0.30 0.48

0.49 0.53

0.37 0.53 6 IO ¹²
8 · K) " ¹

7- K) "
7 · K) "

8 x 10 "

y · ίο "

0 to 10
0

0 to 20
0

0 to K)
0 to 20

Example 7

Of the cooligomers mentioned above !! common structural formula: i ^ oenen

-CH

CHC

-z in

R, Q and Z hydrogen,

Y is an amino group,

X is a phenyl group and

q a phenylene group with nitrogen

containing substituents (i.e. cooligomers consisting of styrene and in aromatic styrene),

Core substituted

were the Cooligomcre, in which the nylon substitute " ¹ -CHjN (CH ₃ ) J · Cl (sample XVIII) or in which the • nylensubstituent -N (C ₂ H ₅ J ₃ · Cl (sample XIX) and TeTn's ^{q em qilaternary} ammonium salt of pyridine -

Cl (sample XX)

"> '. in certain proportions with polystyrene vcrnnsch, be. kneaded about 180 ° C and made into foils vtrpreut. The samples prepared in this way left to carry out the tests 100 days at relative

τ κ ι, ⁸ , ' ^{From 65% sl} chen. The results are ^: "labeile 7 included.

Il

Table 7

XVlIl 26.8

XIX 41.1

XX 32.7

39.2 47.6 49.0

2 2.6 K) ¹³ 5 4.8 10 " 2 7.6 10 " 5 3.1 10 " 2 3.8 10 ^u 5 2.7 · 10 " Example 8

sample quat. Amino Polymeri Per IÜO parts. Spec. Upper Surfaces- Tobacco ash nium group c degree of sation Polystyrene flat frictional test Cooligomer (m / n) added contradicting potential (%) (n) lot (Parts) (U) (V)

10 to 30 10 to 20

10 to 30 0 to 20

10 to 35 10 to 30

Cooligomers of the structural formula given above, in which the phosphoric acid group - PO3H2 (sample XXI), in the aromatic nucleus of the oligostyrene,
the phosphorous acid group - PO2H2 (sample XXII) or
introduced the phosphonamide group (sample XXIII)
and which had been prepared by solvent polymerization had an average degree of polymerization η of 67, and wherein Y and Z
had no particular structure, but presumably
Were hydrogen or other groups of atoms

mixed in ABS (acrylonitrile-butadiene-styrene) resins and pressed with it in the manner described in Example 1 zi foils. The results of the tests performed on the samples at 60% relative humidity are shown in Table 8. The degrees of polymerization / of the samples of the cooligomers XXI, XXII and XXII were 47.6, 28.3 and 28.3 and the proportion of the introduced polar groups m / n 31.6%, 44.9% and 44.9% .

Table 8

Cooligomer per lOOTcile Spec. Obcr- Surface Tobacco ash ABS resin area- frictional test Type added amount resistance potential (Parts) Ui) (V)

XXI

XXU XXIII

5.7 x 10 "
2.4 · 10 ¹⁰

3.2 ■ 10 ^ll)
6.6 10 ''

10 to 40
10 to 25

10 to 25
0 to 30

Example 9
Cooligomers made from styrene and 2-NNN-tri; ethyl-N-chloro-i | uaturn; ir-ammonium-iithyl methacrylate of the formula:

CH ₃ Cl

CH, - = C -COOCH ₂ CH ₂ N (C ₂ II ₅ ).,

were tested in the same manner as in Example I at a relative humidity of 65%. The hearing results are shown in Table 9.

13th

Table 9

Cooligomer

Styrene based

middle
MG

(M)

4000

5050

2960

Treated resin

Fro lOOTcilc

added

lot

(Parts)

G P-PoIy-

styrene *)

Polymethyl

methacrylate

SECTION

AS

G P-polystyrene *)
Polymethyl methacrylate

SECTION

AS

Polymethyl methacrylate

SECTION

2 2

3 3

2 2

4 4

Spcz. Upper

flat

resistance

6.4 x 10 "

8.6 10 '

7.1 · 10 '" 5.7 10 '" 8.2 K) ' ² 7.4 10 " 6.9 10 '" 3.2 10 " 3.3 · 10 ⁹ 4.5- 10 ^U)

14th

Surfaces-

frictional

potcntial

(V)

10 to 30 20 to 40

10 to 30 6 to 25

40 to 100 20 to 60

20 to 40 20 to 50

0 to 20 0 to 20

Tobacco cst

*) GP General Purpose.

Example 10

Cooligomers analogous to the compounds of Example 6, but the oligostyrene derivatives with a degree of polymerization represent π of 42 and wherein

Y, R, Q and Z hydrogen,

X is a phenyl group and

q is phenylsulfonic acid (sample XXIV) or

where q is phenylsulfonic acid stannate (sample XXV), phenylsulfonamide (sample XXVI] or methylphenylsulfonate (sample XXVII) ISt,

were added to GP (multipurpose) polystyrene and the tests of the samples at a relative humidity carried out by 70%. The results are given in Table 10.

Table 10 Styrene per lOOTcile Spec. Upper Surface Tobacco- Cooligomer salary Polystyrene next- frictional ashc- added resistance potentia! test Type lot (%) (%) 5 61.2 5 Ui) (V) 5 8.5 ■ K) ^s 0 to 20 (-) XXlV 5 3.7 K) '" K) until 30 (-) XXV 7.4 · K) " K) up to 40 (-) XXVl 5.2 x 10 '" K) until 30 (-) XXVIl

Claims (1)

Patent claims: 1. Use of oligomers of the general formula: Y- CH ₂ -CH CH-C